Method of and apparatus for hydrogenating fatty acids and their glycerids



am M @/@UT 'AQQHAmss'oN ANU PIBERTHQN. METHOD OFAND PPARATUSFOR HYDROGENATING FATTY ACIDS AND THEIR GLYCERIDSI.

Patented sept. 21; 1920.

APPLICATION FILED JUNE 21, I9I7.

WMZ/mmv? l ffl/Vel//JJZQY a I I' A'. RADISSON ANDP. BEINIIDN.

METHOD DF AND APPARATUSy FoIIA HYDIIDGENATI'NG 4FATTI AcIDsIINDIIIEIII LI/cEII'IDs."

1,353,419; Pmndsept. 21,1920.

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3 f A l 'L'. im iff/(40 l w my @We N N @y WWW v el .A. RADISSON AND P. BEHHDN. METHOD 0F AND APPARATUS FO'H NYDRDGENATING FATTY ACIDS AND HEIR-GLYCERIDS.

, APPLlcAT'IoN man 1uNE`21. i917. j 1,353,419. Patentedsepn 1920.

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FIG; 4- A To all whom it may encarar Fae :El

"aUGU'sTrN anpissen am :eatin isnit'rnon, or LYON; riaiiitciig swamz-m`ss0'N ASSIGNOR TO SOCIETE DE STEAB'NERE FRANCE.

ria' sayonivnnin liin trom-or LYON,

iun'rnon orI ann-Arrenn'rus ron Hvnaoenim'rinefiiairr ecins'iiitn THEIR i e-Lrcnnnsj n iltil application niet June ai,

'- Be it knownthat we,- AUGUs'rIN Buisson and PAUL BERTHQN, both citizens of the French Republic, and residents ofLyon, in

France, have invented a -certaiivnew and' useful Method of and Apparatusfor Hydrogenating Fatty Acids and Their Glycerids,

of which the following is af specification.

This invention relates to .a method for the saturation by means of hydrogenl of unsatuf rated fatty acids and their glycer'ids and apparatus therefor."

- known indicate tures (70 l ing passed through lect of the rNumerous catalytic processes have been suggested for the saturation by hydrogen of unsaturated fatty acids and their glycerids.

The many difficulties encountered in practice-arise either from the catalyzer itself or from the defective conditions of its employ-- ment.

The object of' the present invention isi-to obtain, with a given catalyzer, arational, rapid and complete Vhydiogenation.

lt is known that apart fi'om'the catalyzer itselfthree causes may affect the speed ofa reaction e. the pressure, the temperature,

Various known j processes already made the most variable tempera- 130,230" C.) and working pressures (2 to 15 kilos). 'Diicultisin the construction of an apparatus for the use of hot hydrogen at high pressure lead to the neglatter factor for increasing the speed of reaction. t

Now sin-cenni object ofthe invention is vto obtain'the maximum speed .of reaction, and

v any isothermic reaction at constant pressure lbeing a reaction at decreasing speed, the;

temperature of the reagents must be progres- ,Isively-raised in the course of the operation.

Under these conditions, in'orderrto avoid the extremely injurious reactions of hydrolysis and obtain products 'of special purity,#in particular products intended for food-the hydrogen is purified and dried in a thorough manner by asuitable process,

for instance an A,energetic cooling to about Moreover, although hydrogen has relatively a very slight density, still after hav-` y a mixture of glycerids and free fatty vacids not completely satu-` rated it carries with it a certain quantity of the most volatile products,\which areactuany the .fatty acids.

Consequently,ik ifl the saturation iseffected omglycerids containing a` small proporonof fatty acids, almost the whole of these latter will be eliminated during the y eration ofhydrogenation; if,\on the ontrary, fatty acids are treated which are not completely saturated and which form the mostjimportant part of. the substance treat! ed, the other compounds being in small proportion in relation to the fattyvacids treated, a small part only oftheseffatty acids can be Sieecation of Letters Bait-ent. l "Pat-@m4543451 Spha' 219192@ time. (averaging three hours) ofropcarried away by the surpliis hydrogen' which I "leaves the apparatus'atliese fatty acids eX- tracted willbe'complgetcly saturated in the presence ofthe 4hydrogen which carries them' outof the digester and they'can then be con-g' densed in a hydrogen. purifying apparatus,

Awhile the greater part-ofthe fattyacids will be saturated in the digester itself. The .processtherefore allows glycer'ids to be'puriied which contain a slight acid without preventing eflicacious'and economical treatment of the lfatty.- acids contain# ing or not containing impurities. ln both eases, the fatty acids extracted, the quantity of which depends only on plus hydrogen passing through the; appa! ratusyare, .condensed in the purifier/orreytained by caustic soda, before again putting the surplus hydrogen in 'circulaQ-tion.

With hydrogen thus absolutely -diy and *proportionI of fatty pure, almost the whole'of` theffatty acids A contained -a's impurities in a given amount of glycerids will be tures and-pressures contemplated; Starting with products containing l to'` per cen-t, of acidity these be" found to contain no more than 0.5-"'per cent. of acid at the most, and notcontain any dissolved catalyzing metali'f.'l Conse-4 lquently, I Aof neutralization Willbe avoided.

Further, the fatty acids 'extractedaiielcon;

densed in a suitable apparatus eitherto the free state or a statev of chemical lcombination as hereinbefore indicated.

roducts after treatment will' distilled i at. the tempera- A u the long and troublesome operations rIhre contact between the reagents isiregu?,

lated' according to the working temperature. At the temperatures proposed'ytthe colloidal solution of the catalyz'ei' in. the oils or fatty acids is-quiclrly destroyed, especially inftlie latter. ln order to prevent this', thecata- 'lyzer is progressively injected in a suitable form in proportion as the reaction tends to slacken. Thus the amount of catalyzing agent is constantly increased in the apparatus as the proportion of unsaturated glycerids or fatty acids diminishes, which maintains to a suflicient amount the number of contacts in the unit of volume of matter under treatment.

1. The addition of catalyzer is effected at the rate of progress of the reaction,by means of the apparatus 33. lnto this apparatus 33 can be introduced the amount ofl catalyzer sufficient for an operation, andthe catalyzer can be injected gradually by meansof the hydrogen under pressure7 so as to' progressively increase the proportion of catalyzer.

ess and particularly for products intended for food. lnthe drawings Fig. 2 is a con-` tinuation of Fig. 1 fromthe dotted line A1- A. Fig. 3 is a continuation of Fig.2

from line B-B and Fig. .4 a continuation v pf Fig'. 3 from line C--Cj Fig. 5 is a detail View oir/a larger scale y of a digester.

The digesters 1' and 2 Working alternately or inparallel are heated by means of a ldouble casing 3 around which circulates a suitable caloric vehicle (superliea'ted steam, heavy oils,vaseline) which enter at 4 and pass out at 5 and is distributed by means of a series of partitions 6. The rate of admission of this heating agent to the jacket is so regulated, by means of the inlet valve, that the required progressiveraising'of the temp'erature is obtained.

The oils to be hydrogenized, introduced through the pipe 7 into one of the digesters are brought to the priming reactioiitemperature varying as the case may be 'from 180O to 220O C. The hydrogen is then forced by means of the compressor 2O into the bottom `of the apparatus at a pressure just suflicient to overcome the resistance of the oil and of.

the condensing and Washing apparatusvl (about 1 kilo).

The unabsorbed gas escapes at the top of- 1 and passes into the-temperature exchanger 8, comprising .a simple tubular group 8l Where it imparts its heat to the hydrogen coming from the reservoir 9 which, intro duced at 10, issues'at 11. The` plates 12 dis- I' tribute lthe gas uniformly around the tubes 8a. This exchanger serves as to automatically regulate the temperatureof the hydrogen introduced into the digesters. lin fact, during -the reaction of hydrogenation, which ,dis-

' charges with certain oils largequantities of heat, the greaterpart of the hydrogen is instantaneously absorbed. The amount of hyleaving the digester 1 the hydrogen carries.

Withit'a large amount of free fatty acids. The latter are condensed firstly in the tem` perature exchanger 8 and then in tubular condensers 13, 14 regularly cooled, the Water having circulated in 14 then entering into 13.

This distiilation of the fatty acids carried off by the dry hydrogen enables the. operations of neutralization to be dispensed with in the case ofaalimentary-fats.

' On leaving the condensers the gas )asses through the 4chamber 15 provided Wit perforated plates 16 and containing caustic soda, Which absorbs certain volatile impurities of the oils. The hydrogen passing out from the chamber 15 is freed, in the Waterv separator 17, fromr the liquid mechanically acquired. i

Finally, in order to eliminate the last traces of impurities andA at the. sametimeA bring the gas to the condition of absoluted desiccation, it is caused to circulate in a temperature exchanger 18 of the same type asA the apparatus -3 WhereA its temperature is equalized tothat of the gas passing out from the cooler19.

llt then passesintoi'the cooler itself, coin` posed of an ordinary tubular group, cooledv by means of a suitable process to the temperature off-'200. `The amount of cold to be supplied to the gas being very small a small refrigeratorv will be suiiicient to give suitable results. The apparatus shown fory this purpose in Fig. 4 comprises a carbon dioXid or .sulfurous acid ice machine 41, a condenser 42 for the liquefied gas, a'tank 43 for therefrigerating solution, and a pump 44 connected by a pipe 45 to the cooler 19. i The gas on leaving the cooler 19 circulates in the jacket ofthe apparatus 18 around the tubular group and is warmed `in"contact With the gas flowing from the purifier. j,

This hydrogen thus freed from all traces of moisture and impurities is sucked in by the compressor 20 and `again drivenw into the digesters. The gas absorbed during thereaction is replacedA by pure gas supplied, for instance, by an electrolysisbattery. This added gas'is compressed to 2O kilos by the .compressor 21 in a reservoir 22 cooled by means of the circulation of Water in a'l serpentine pipe 23.

This compressed hydrogen is thus ab-- .i

solutely dry, as the Water condenses in tlie bottom of the reservoir. It is introduced by means of an expander 24 into the reservoir 9y in passing through a Water separator 25,

` perfect contact between the reagents, at the distribution of the catalyzer.

same time as the progressive and methodical and distributed by a lanterns-pipe 27 with four openings and passes through the holes ,of the sprinkler 28. lt breaks against the Y' methodically .2.5 of acidity,

c during a rather short period of time it is graduaily temperature parabolic member 29 provided with heli- L0 coidal blades 30 imparting a helical move mentto the mixture of gas and oil Above the member 29 is an injector 31 in which the catalyzer mixture is introduced through the nozzle 32. This mixtureisprepared in the apparatus 33,

vided With an energetic agitatingl device bafiies 35.

The reduced catalyzing ymetal is introduced through the' funnel 36 'and by the pressure of hydro en conducted through a tube 37 the cataytio mixture is forced through the lower tube 38 into the in? jector 31. .l

' @Wing to this device the catalyzer can be introduced and the course of the reaction thus regulated. This progressive addition has moreover the advantage of maintaining the colloidal solution ofthe catalyzer in the oil and consequently perfect contact between the reagents. f rlhe catalyzer when freed vfrom the oil by any means (a drier 30 Fig. 3y for instance), can be used many times.

Example l: 5,000 kilos'of soy oil of 0.7 acidity are introduced into the digester and heated to 200o C. After starting thegaseous current the catalyzer is introduced little by litt e." The reaction is started and the tem` per: ture is raised lby degrees While large quantities of hydrogen are absorbed. Thus in three hours a product is obtained attaining 54 of .fusion point. The tempera-l ture has been able to riseld'uring ,the course of the reaction up to 300 C. The vproporfv tion of catalyzer employed has not exceeded 0.5 per cent. 650 m3 of hydrogen has vbeen absorbed and the acidity of the product hardly a'tt'ains 0.2. e

Example H: 5,000 kilos of Whale oilof are introduced into the digester which is heated to 170o C., at Which I. the addition of the catalyzer is commenced.

Any suitable heating means may be em! ployed which allow the temperature of the oii to be varied Within' the limits of 30"` t@ e500 C.

rhe initial temperature is i703 5 first rises from the fact of the reactie raised by the addition of external hea an" by the course c? tion. up temperature@ Which has a double bottom heated by steam to about 180o C. and pro- 1 'Lillie reaction is .Veryviolent at the commencement and tends to become quieter but* is lievived by theA proper 'quantitiesof cataof 473 C. isn

product 1s suitable for alimentation. 500 m3.

o f hydrogen 'hasbeen absorbed.

What We rclaim as our invention vantidesire to secure by Letters Patent of the United States is 1. In the process of saturating -un'saturated fatty acids or their glyceri'ds by means of hydrogen in the presence of a catalyzer, maintaining a constant speed of reaction vby the progressive addition of external'kheat, and increasing the amount of catalyzer as the proportion of unsaturated fatty acids or glycerids decreases.l 2.V n apparatus for saturating unsat-urated fatty5 acids'or their glycerids by means of -hydrogenithacombination of a digester, adouble jacket' therefor, means for thel introduction of a heating agent into said jacket, a verticaly chamber horizontal gas distributing `plates in said chamber, open ended vertical tubes insaid chamber passing through said plates a hydrogen supply condut.connected to said chamber above the lower end of said tubes,.a hydrogen conduit. connecting the lower part ofthe digester to said chamber below the upper end-'of said tubes, and a hydrogen conduit connecting the upper part of the .digester to said chamber above the upper ends of said tubes.

` 3.vv An apparatus'for the saturation of unsaturated fatty acids and their glyceri'ds by means of hydrogen, comprising a digester, meansfor heating said digester, means for introducing the oils to be' hydrogeivgiized into said digester, means for introducing hydrogen under pressure into said digesterand means -for automatically regulating the temperature of the hydrogen introduced into said digester,'means forK4 the outlet. of the vhydrogen containing fatty acids from said dgester, means'forcondensing said fatty acids, meansv ties in the fattyracids, means for drying and cooling said h drogen, means for again Warming said and .means for the progressive introduction of the catalyzer to said digester.

4. An apparatus for the saturation of un- Asaturated .fatty Aacids and their glycerids by -means of hydrogen, comprising a digester,

ydrogen, means for reintroducing said hydrogen into said 'digester for absorbing volatileimpuri matically: regulatingI the temperature of `theV hydrogen introduced into said digester, comprising a vertical chamber, Vertica1openended tubes in said chamber, plates for distributing the hydrogen gas in said chamber, and means for the'introduction into and outlet of the gas from said. chamber: means for the outlet ofthe hydrogen containing ifatty acids from said digester,

means for condensing said fatty acids,v means for absorbing volatile impurities'in the fatty acids, means for drying and cooling said'hydrogen, means for `again Warm-- ing saidr hydrogen, means for reintroduc` ing said hydrogen into said digester, a oham-` lmixture lfrom troducing vthe eatalyzing metal into said last mentioned chamber, means for heating said f chamber, an a'gitating device in said chamber and means for conveying the catalytic `said lohambervinto said diges'ter. Y

In Witness Wherfeofy We have signed this specification in the presence of two Wit.

nesses. 4

UGUSTN RADISSON-- PAUL BERTHQN. Witnesses:

JEAN GERMAIN, MARIN VAoHoN. 

